Synthesis and characterization of 1-azido-2-nitro-2-azapropane and 1-nitrotetrazolato-2-nitro-2-azapropane

Abstract

1-Azido-2-nitro-2-azapropane (1) was synthesized in high yield from 1-chloro-2-nitro-2-azapropane and sodium azide. 1-Nitrotetrazolato-2-nitro-2- azapropane (2) was synthesized in high yield from 1-chloro-2-nitro-2-azapropane and silver nitrotetrazolate. The highly energetic new compounds (1 and 2) were characterized using vibrational (IR and Raman) and multinuclear NMR spectroscopy (1H, 13C, 14N), elemental analysis and low-temperature single crystal X-ray diffraction. 1-Azido-2-nitro-2-azapropane (1) represents a covalently bound liquid energetic material which contains both a nitramine unit and an azide group in the molecule. 1-Nitrotetrazolato-2-nitro- 2-azapropane (2) is a covalently bound room-temperature stable solid which contains a nitramine group and a nitrotetrazolate ring unit in the molecule. Compounds 1 and 2 are hydrolytically stable at ambient conditions. The impact sensitivity of compound 1 is very high (< 1 J) whereas compound 2 is less sensitive (<6 J). The molecular structure of 1-azido-2-nitro-2-azapropane (1) in the crystalline state was determined by X-ray crystallography: orthorhombic, P212121, a = 0.57775(1) nm, b = 0.65782(1) nm, c = 1.53472(3) nm, α=β = γ = 90.0°, V=0.58329(2) nm 3, Z=4, Q = 1.493 g cm-3, R1 =0.0386 (all data), wR2 (all data) = 0.0931. The molecular structure of 1-nitrotetrazolato-2-nitro-2-azapropane (2) in the crystalline state was determined by X-ray crystallography: monoclinic, P21, a = 0.60615(2) nm, b = 0.58921(2) nm, c = 1.10733(5) nm, α = γ = 90.0°, β = 100.465(2)°, V=0.38890(3) nm3, Z = 2, Q = 1.735 g cm -3, R1 = 0.036 (I>2σI), wR2 (all data) = 0.085. © 2006 WILEY-VCH Verlag GmbH & Co. KGaA.